Planar Pd Research Articles

Does alpha-fluorination affect the structural trans-influence and kinetic trans-effect of an alkyl ligand? Molecular structures of Pd(TMEDA)(CH(3))(R(F)) and a kinetic study of the trans to cis isomerization of Pt(TMEDA)(CH(3))(2)I(R(F)) [R(F) = CF(2)CF(3), CFHCF(3), CH(2)CF(3)

Reaction of Pd(TMEDA)(CH(3))(2) [TMEDA = tetramethylethylenediamine] with fluoroalkyl iodides R(F)I affords a series of square planar Pd(II) complexes Pd(TMEDA)(CH(3))(R(F)) [R(F) = CF(2)CF(3) (9), CFHCF(3) (10), CH(2)CF(3) (11)], presumably by oxidative addition followed by reductive elimination of CH(3)I. The solid-state structures of each compound have been determined by single crystal X-ray diffraction studies, allowing the effect of increasing alpha-fluorination on the structural trans-influence of alkyl ligands to be examined. In these compounds there is no significant difference observed in the trans-influence of the three fluorinated alkyl ligands toward the trans-N atom, although a significant cis-influence on the neighboring methyl ligand is apparent. Oxidative addition of the same series of fluoroalkyl ligands to the corresponding Pt(TMEDA)(CH(3))(2) affords octahedral Pt(IV) complexes trans-Pt(TMEDA)(CH(3))(2)(R(F))I [R(F) = CF(2)CF(3) (12), CFHCF(3) (13), CH(2)CF(3) (14)] as the kinetic products. In each case, subsequent isomerization to the corresponding all cis-isomers is observed; in the case of 13, the stereocenter at the alpha-carbon results in two diastereomeric cis-isomers, which are formed at different rates. The molecular structures of 13 and its more stable all cis-isomer 16b have been crystallographically determined. Kinetic studies of the trans-cis isomerization reactions show the mechanism to involve a polar transition state, presumably involving iodide dissociation, followed by rearrangement of the cation, and iodide recombination. High dielectric solvents increase the rate, but solvent coordinating ability has no effect. Dissolved salts (LiI, LiOTf) show normal accelerative salt effects, with no inhibition in the case of added iodide, consistent with the formation of an intimate ion pair intermediate. The kinetic parameters show that the trans-effects of fluoroalkyl ligands in these compounds follow the order expected from the relative sigma-donor properties of the ligands, with CF(2)CF(3) < CFHCF(3) < CH(2)CF(3).

NaPdPS 4 and RbPdPS 4: systems with infinite straight [formula omitted][PdPS 4] − chains soluble in polar solvents and the structure of cubic RbPdPS 4{Rb 0.33P 0.4S 2.23O x}

The synthesis, crystal structures, chemical and spectroscopic properties of NaPdPS 4, RbPdPS 4, and RbPdPS 4{Rb 0.33P 0.4S 2.23O x } are described. NaPdPS 4, RbPdPS 4, are isostructural and crystallize in the tetragonal system I4/ mcm with cell parameters a=7.3074(8) Å, c=12.2308(14) Å and a=8.2954(3) Å, c=12.2284(4) Å respectively. RbPdPS 4{Rb 0.33P 0.4S 2.23O x } is cubic, space group Pm-3 n and a=12.0042(2) Å. All compounds contain the same 1 ∞ [PdPS 4] − chains made of alternating square planar Pd 2+ cations and tetrahedral [PS 4] 3− anions. RbPdPS 4{Rb 0.33P 0.4S 2.23O x } contains co-crystallized highly disordered molecular species encapsulated within [Rb 8] cubic cavities. Spectroscopic solid state 31P NMR, infrared and Raman data as well as elemental analysis suggest that these species could be S n 2− ( n=3 or 4) anions and possibly cationic [P 4S 6O] 6+ fragments. NaPdPS 4 and RbPdPS 4 exhibit exfoliative dissolution in polar solvents giving rise to solutions that show signs of complex fluid behavior.

Outer sphere anion participation can modify the mechanism for conformer interconversion in Pd pincer complexes

Interconversion of the two chiral conformations of the square planar Pd(II) CCC pincer carbene complex, 1 (η3-C,C′,C″) (2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}phenyl)bromopalladium(II), and the CNC cation, 2, (η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)bromopalladium(II)(1+), is characterized by VT NMR spectroscopy. Combined DFT/experimental work indicates two alternative mechanisms. In the case of 1, having no counterion, and several derivatives of 2 with weakly nucleophilic counterions, the fluxional process goes in two steps via an unsymmetrical cationic 4-coordinate intermediate. In this case one carbene ring moves through the square plane before the other. In some cases for 2 with more nucleophilic counterions, such as [{CNC}PdI]I, a second lower-barrier process takes over that depends on the nature of the counterion. We propose that the outer sphere anion reversibly displaces the central N (pyridine) unit of the pincer in a rate limiting step to form a neutral dihalo intermediate that undergoes rapid conformer interconversion. This accounts for the counterion dependence and constitutes an unusual type of fluxionality that couples anion substitution at the metal with the conformational change of the ligand. A pyridine, even when present as the central element of a CNC pincer ligand, can therefore be labile even under mild conditions and reaction mechanisms involving decoordination of such group are therefore possible.

Synthesis and crystal structure of 〚PdMe{PPh 2NHC(O)Me}{O=C(NH 2)Me}〛〚BF 4〛, a palladium complex containing the acetamide ligand

The synthesis of a square planar cationic Pd(II) complex containing the acetamide ligand is described. The complex has been characterised by X-ray diffraction, leading to one of the rare examples of a crystal structure showing an acetamide molecule coordinated to a metal centre and, to the best of our knowledge, the first one with palladium. This complex may be relevant to catalytic reactions, such as the palladium-catalysed amidocarbonylation, in which transient species with O-coordinated acetamide can be formed.

Metal complexes of 4′-(3-phenylpropoxy)-2,2′:6′,2″-terpyridine and 4′-(3-propoxy)-2,2′:6′,2″-terpyridine

Reaction of 4′-chloro-2,2′:6′,2″-terpyridine with 3-phenyl- n-propanol or n-propanol in the presence of excess KOH in dmso, respectively, yields 4′-(3-phenylpropoxy)-2,2′:6′,2″-terpyridine (L 2) and 4′-(3-propoxy)-2,2′:6′,2″-terpyridine (L 3). The following complexes of these two ligands have been prepared: [{Cu(μ-Cl)L} 2](BF 4) 2, [Cu(NCMe)(L)](BF 4) 2, [PdCl(L)]BF 4 and [PtCl(L)]BF 4 (L=L 2, L 3). Recrystallisation of [Cu(NCMe)(L 2)](BF 4) 2 from PhCN/Et 2O yields [Cu(NCPh)(L 2)](BF 4) 2, whose crystal structure shows a square planar Cu(II) ion with substantial disorder in the PhCN ligand and 3-phenylpropoxy tail. The single crystal structure of [PdCl(L 2)]BF 4·2CH 3NO 2 contains a square planar Pd(II) centre. Neither of these structures, nor the solution spectroscopic or electrochemical data from the complexes, provide any evidence for intramolecular π–π interactions between the terpyridine ring and phenylpropoxy substituent. (Non-SI unit employed: 1 G=10 −4 T.)

Synthesis, solution and solid-state structure of Pd(II), Pt(II), Ir(III) and Zn(II) complexes with 5-pyridyl substituted N-methyl isoxazolidines

Pd(II), Pt(II), Zn(II) and Ir(III) complexes with 5-pyridine substituted N-methyl isoxazolidines (4-(2-methyl-3-phenylisoxazolidin-5-yl)-pyridine ( L 1 ), 2-(2-methyl-3-phenylisoxazolidin-5-yl)-pyridine ( L 2 ), 2-(2-methyl-3-ferrocenylisoxazolidin-5-yl)-pyridine ( L 3 )) have been prepared and characterized by 1H, 13C, and 31P NMR. The configurations of coordinated isoxazolidines have been assigned by the analysis of NMR coupling constants and by nuclear Overhauser measurements through 2D-ROESY experiments. The molecular structures of [Cp*Ir( L 2 )Cl][BPh 4] ( 6) (Cp*-pentamethylcyclopentadienyl) and trans-[PdCl 2( L 3 )PEt 3] ( 8) have been established by means of X-ray crystallography. The crystal structure of 6 consists of piano stool geometry with respect to the Ir(III) center with N, N-bidentate coordinated ligands. The six-membered chelate ring formed by Ir(1), N(1), C(5), C(6), O(1), N(2) possesses a ‘twist-tub’ conformation. The crystal structure of 8 consists of neutral square planar Pd(II) complexes. L 3 is coordinated in a monodentate manner via the pyridine nitrogen atom. The isoxazolidine fragment of both compounds has an envelope conformation. NMR data are consistent with an O, N-bidentate coordination of L 2 for [Zn( L 2 )Cl 2] ( 5), while L 1 act as a monodentate ligand through the nitrogen atom of the pyridine in [Zn( L 1 ) 2Cl 2] ( 4).

Vibronic structure in the luminescence spectra of tetragonal d2 and d8 complexes analyzed by wavepacket dynamics on two-dimensional potential surfaces

The luminescence spectra of the tetragonal trans-ReO2(vinylimidazole)4+ complex and the square planar Pd(SCN)42? and Pt(SCN)42? complexes all show vibronic progressions in two predominant vibrational modes. In the first complex, the vibronic progressions involve high-frequency and low-frequency metal?ligand modes. In the square planar complexes, the two vibrational modes have similar frequencies. At the intermediate resolution, often observed experimentally, these compounds provide an example of the missing mode (or MIME) effect. Wavepacket dynamics on two-dimensional surfaces explain in a visual and intuitively appealing way the spectroscopic features. The distinct effects are caused by the different frequency ratios between the two modes of the two-dimensional models describing each complex. The emitting state structure determined from the spectra reveals similar changes along a bending normal coordinate for Pd(SCN)42? and Pt(SCN)42?

Synthesis and X-ray crystal structure of dipalladiumtetrachlorobis(ethyldipyrrolylphosphine)

The ligand ethyldipyrrolylphosphine and the corresponding palladium(II) complex, [PdCl{PEt(pyrrolyl) 2}μ-Cl] 2, were synthesized. The X-ray single-crystal structure of this palladium complex was determined; it crystallizes in the monoclinic space group P2 1/ n with a = 15.347(7), b = 11.212(6), c = 17.355(5) Å and β = 115.72(3)° and contains a central pseudo square planar Pd 2Cl 4 ring having a trans conformation of N-pyrrolyl phosphines. The arrangement of the pyrrole substituents around the phosphorus atom in the complex clearly shows the inaccessibility of the α-carbon for polymerization.

Reactivity of a stepped surface NO dissociation on Pd(211)

Pathways for the dissociative adsorption of NO on the planar Pd(111) and the stepped Pd(211) surfaces are calculated using density functional theory. The pathways with the smallest energy barriers for the dissociation are found to be very similar on the two types of Pd surfaces. The stepped surface exhibits the smallest energy barrier, because this surface binds the molecular NO and the atomic N and O, more strongly than does the flat surface.

Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of K(4)Pd(PS(4))(2), Cs(4)Pd(PSe(4))(2), Cs(10)Pd(PSe(4))(4), KPdPS(4), K(2)PdP(2)S(6), and Cs(2)PdP(2)Se(6).

The reaction of Pd with a molten mixture of A(2)Q(x)()/P(2)Q(5)/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K(4)Pd(PS(4))(2) (I), Cs(4)Pd(PSe(4))(2) (II), and Cs(10)Pd(PSe(4))(4) (III) and the solid-state KPdPS(4) (IV), K(2)PdP(2)S(6) (V), and Cs(2)PdP(2)Se(6) (VI). Compounds I-III are air and water sensitive, while IV-VI are air and water stable. All crystals are red or dark red except those of VI, which are black. All of them exhibit a rodlike shape. Compound I crystallizes in the triclinic space group P&onemacr; (No. 2) with a = 6.380(1) Å, b = 6.897(1) Å, c = 8.999(1) Å, alpha = 87.777(8) degrees, beta = 81.581(8) degrees, gamma = 84.429(9) degrees, and Z = 1. Compound II crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 7.491(2) Å, b = 13.340(2) Å, c = 10.030(3) Å, beta = 92.21(2) degrees, and Z = 2. Compound III crystallizes in the tetragonal space group P&fourmacr;2c (No. 112) with a = b = 13.949(2) Å, c = 11.527(2) Å, and Z = 4. Compound IV crystallizes in the tetragonal space group P4(2)/mnm (No. 136) with a = b = 8.5337(2) Å, c = 10.5595(5) Å, and Z = 4. Compound V crystallizes in the orthorombic space group Pnma (No. 62) with a = 15.612(2) Å, b = 7.0724(7) Å, c = 10.080(1) Å, and Z = 4. Compound VI crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.9750(4) Å, b = 8.3282(2) Å, c = 13.0568(1) Å, beta = 102.940(2) degrees, and Z = 4. Compounds I-III contain the discrete complexes [Pd(PQ(4))(2)](4)(-) (Q = S, Se). The mixed salt III contains additional noncoordinating [PSe(4)](3)(-) units. The structure of IV consists of Pd(II) in square planar sulfur coordination linked by edge-sharing [PS(4)](3)(-) tetrahedral groups to produce one-dimensional chains. The structures of V andVI feature the [P(2)Q(6)](4)(-) (Q = S, Se) group coordinated to the square planar Pd(2+) atoms, yielding [PdP(2)Q(6)](n)()(2)(n)()(-) chains. Physical characterization was performed with DTA, far-IR spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical transmission.

Synthesis and characterisation of Pd(II), Pt(II) and Pt(IV) complexes of diphosphadithia ligands and the crystal structure of [Pt(L 1)] (PF 6) 2·MeCN (L 1Ph 2P(CH 2) 2S(CH 2) 2 S(CH 2) 2PPh 2)

A series of square planar Pd(II) and Pt(II) complexes involving tetradentate diphosphadithia ligands has been prepared in high yield and characterised by IR, 1H, 31P( 1H) and 195Pt NMR spectroscopy, mass spectrometry and microanalyses. [Pt(L 1)] 2+ (L 1Ph 2P(CH 2) 2S(CH 2) 2S(CH 2) 2PPh 2) crystallises in the triclinic space group P I (No. 2), with a = 12.644(8), b = 15.15(1), c = 10.368(6) A ̊ , α = 94.16(5), β = 105.24(5), γ = 86.53(5)° and Z = 2 . The structure confirms the distorted square planar coordination at Pt(II). PtP = 2.261(2), 2.265(2), PtS = 2.341(2), 2.344(2) Å. The geometry is rather strained, with the methylene groups all directed to one side of the coordination plane and the metal ion displaced out of the least squares P 2S 2 plane by 0.19 Å in the opposite direction. Halogen oxidation (Cl 2 or Br 2) of the Pt(II) species yields the cationic Pt(IV) compounds [PtX 2(L)] 2 as yellow (Cl) or orange (Br) species. 31P 1H and 195Pt NMR studies confirm that the P 2S 2 ligation is retained, giving octahedral P 2S 2X 2 coordination at Pt(IV), in which the relatively hard Pt(IV) centres are stabilised by a soft ligand donor set.

Aliphatic cyclopalladation. Crystal structure of

Cyclopalladation of 2,6-dimethyl- N-(2′,4′,6′-trimethyl-benzylidene) aniline ( 1) in refluxing acetic acid followed by reaction with excess LiX affords the dinuclear ▪ ( X = Br ( 2 a ), I ( 2 b )), which contain six-membered palladacycles. Compound 2a crystallizes in the monoclinic space group C2/ c, with a = 18.879(3), b = 19.044(3), c = 10.169(2) A ̊ , β = 117.04(2)° and Z = 4 . The overall geometry of 2a includes a planar Pd 2Br 2 rhomboid and a syn arrangement of the free phenyl rings of cyclometallated ligands.

Wasserlösliche Phosphane V. Komplexe amphiphiler tertiärer alkylphosphane mit Ammoniumgruppierungen in den seitenketten

Monocationic amphiphilic tertiary phosphines [RMe 2N-(CH 2) n-PR ′ 2] + X − ( 1–3) obtained by P-alkylation of the corresponding primary phosphines (R′  H) form stable tungstencarbonyl-, Rh(I)-olefin- and square planar Pd(II)-complexes ( 4–8a). Stepwise protonation of [Me 2N-(CH 2) 2] 3P ( 9) by Ph 3P · HBr or aqueous HCl affords tricationic tertiary phosphine ligands, e.g. {[HMe 2N-(CH 2) 2] 3P} 3+ 3X − ( 13, 13b) and the phosphonium salt {[HME 2N-(CH 2) 2] 3P-H} 4+ 4Cl − ( 13a). The pK a-values 9.67, 8.86, 7.92 and 1.9 have been obtained by titration of 13a with NaOH in aqueous solution. Highly charged Pd(II)-complexes ( 16a, 16b) with extreme water solubilities were obtained from 13 and PdBr 2 or by N-protonation of cis-PdCl 2(9) 2 with HCI. The crystal structures of 13 · 0.5H 2O and { trans-{[HMe 2N-(CH 2) 2] 3P}) 2PdCl 2} 6+ 6Cl −· 2MeOH ( 16b) (space group C2/c) have been determined. While the P( … N) 3 skeleton of the trication in 13 is almost flat, it is folded back on coordination to palladium(II) in 16b.

Oxidative addition of organic halides to zerovalent palladium complexes containing rigid bidentate nitrogen ligands

Zerovalent complexes of the type Pd(Ar-BIAN)(alkene), i. e. complexes containing the rigid bidentate nitrogen ligands bis(arylimino) acenaphthene (Ar = p-Tol, p-MeOC 6H 4, o-Tol, o, o′-Me 2C 6H 3, o, o′- iPr 2C 6H 3) and an electron-poor alkene have been shown to react with a variety of (organic) halides RX, including methyl, benzyl, aryl, acyl and allylic halides, to give the corresponding square planar divalent Pd(R)X(Ar-BIAN) or [Pd(η 3-allyl)(Ar-BIAN)]X complexes. The new complexes obtained have been fully characterized and their fluxional behaviour in solution studied by 1H NMR spectroscopy. The rate of oxidative addition of iodomethane to Pd( p-Tol-BIAN)(alkene) complexes was found to decrease with increasing Pd-alkene bond strength, i. e. dimethyl fumarate ⪢ fumaronitrile, but oxidative addition to the fumaronitrile complex was accelerated by irradiation with a mercury lamp. Oxidative addition of allylic ha

The insertion of acetylene into the palladium carbon bond of square planar Pd(II) complexes: a theoretical investigation

Ab-initio SCF, CAS-SCF and CI calculations have been carried out for the acetylene insertion into the PdC bond of the [PdCl(NH 3)(CH 3)(C 2H 2)] model system. The acetylene is found to bind quite weakly to the palladium atom and inserts with an activation barrier of 17 kcal mol −1. The geometry of the transition state corresponds to a monohapto coordination of the acetylene. No intermediate seems to be involved on the reaction path, at least for the C 2H 2 system. The effects of substitution of one hydrogen atom by more electron attracting substituents and of a CH group by a metal organic entity are briefly analysed. The stereochemical course of the reaction is also investigated in connection with the geometry of the various isomers known for the isolobal C 3H 5 + organic system.

Synthese und Koordinationschemie hemilabiler P,N‐Hybridliganden mit terminalen 2‐Pyridyl‐Donorgruppierungen

Synthesis and Coordination Chemistry of Hemilabile P,N‐Hybride Ligands with Terminal 2‐Pyridyl Donor Groups*P,N‐hybride ligands 1–7 containing terminal 2‐pyridyl donor groups have been obtained by base‐catalyzed addition of diphenylvinylphosphane or 2‐vinylpyridine to primary or secondary phosphanes [2‐Py‐(CH2)2‐PR′H (R′ = H, Ph), HMeP‐(CH2)3‐PMeH] or by alkylation of organolithium phosphides, R2P‐(CH2)3‐PMeLi or 2‐Py‐(CH2)2‐PR′Li (R = Ph, iPr; R′ = H, Ph), with 2‐(2‐chloroethyl)pyridine or di‐tert‐butylphosphetanium bromide. Upon reaction with NiBr2 3 H2O or K2MCl4 (M = Pd, Pt) the phosphanes (L) of type 2‐Py‐(CH2)2‐P(R′)‐(CH2)m‐PR2 (1, 3, 6) form square planar Ni(II), Pd(II), and Pt(II) complexes of composition MX2(L) (10–14). With NiBr2 and K2MX4 the tripod type phosphane 2 forms square pyramidal complexes [MX(2)]X (M = Ni, Pd; X = Cl, Br; 15, 16). An X‐ray structural analysis of [NiBr(2)]+Br− (15) reveals a distorted square pyramidal coordination geometry at Ni(II), the 2‐Py donor being in apical position with a long NiN bond [2.270(15) Å]. The tetradentate ligand 7 forms Ni(II), Pd(II), and Pt(II) complexes MX2(7) which for M = Pd, Pt show dynamic behaviour by exchange of the terminal Py donor groups. With [RhCl(COD)]2 the tridentate ligands L (1 and 3) yield complexes of composition RhCl(L) (20, 21). The structure of 20 has been determinated by X‐ray diffraction. The ligand 3, acting in a tridentate manner, is coordinated to Rh(I) in a distorted square‐planar arrangement with a normal RhN distance [2.145(3) Å].

Cis-Dichloro[1,2-bis(dicyclohexylphosphino)ethane]palladium(II)

The structure of cis-PdCl 2 (dcpe), where dcpe is 1,2-bis(dicyclohexylphosphino)ethane, [PdCl 2 (C 26 H 48 P 2 )], consists of an approximately square planar Pd II ion coordinated by a chelating dcpe ligand and two Cl - ions. The coordination sphere of the Pd shows a slight tetrahedral distortion. A significant trans influence of the dcpe ligand on the Pd-Cl distances is evident

Synthesis and reactions of cyclopentadienyl complexes containing a palladium carbon σ-bond

Cyclopentadienyl complexes of the type Pd(η 5-C 5H 5)(CH 2Z)(PPh 3)(Z = COC 6H 5 ( 1), COCH 3 (2), COCH 2CI ( 3), CN ( 4) and SCH 3 ( 5)) have been prepared and characterized. The chemical shift of the methylene protons bound to palladium are briefly discussed. The complexes 1–3 react with dry hydrogen chloride to give Pd(η 5- C 5H 5)Cl(PPh 3) ( A) as an intermediate and finally a dimeric complex [PdCl 2(PPh 3)] 2 ( B). Complex 4 also reacts with dry hydrogen chloride to yield [Pd(CH 2CN)CI(PPh 3)] n as an intermediate. Similar treatment of 5 produced a square planar complex Pd (CH 2S CH 3)CI(PPh 3).

Synthesis and easy racemisation of an atropisomerically chiral phosphinamine

Both the chelating P N ligand 1-(2′-diphenylphosphino-3′,6′-dimethoxyphenyl-isoquinoline and its square planar Pd complex ( 15) atropisomerise readily at room temperature.

Investigation of the atomic structure and visibility of crystal/amorphous interfaces in Pd 80Si 20 alloy by HRTEM image simulations

Atomic models of isolated crystalline Pd 3Si embedded in amorphous Pd 80Si 20, a planar crystalline Pd 3Si/amorphous Pd 80Si 20 interface and a faceted crystalline Pd 3Si/amorphous Pd 80Si 20 interface were constructed using a dense random packing (DRP) model for the amorphous alloy. Multislice programs were used to simulate high-resolution transmission electron microscope (HRTEM) images of these models for a JEOL 4000EX microscope. The simulated images show that amorphous alloy superimposed on crystalline Pd 3Si degrades the crystal image. The visibility limit of crystalline Pd 3Si embedded in amorphous Pd 80Si 20 occurs for an amorphous/crystal thickness ratio of about 3.4 near optimum defocus (- 50.0 nm), but this can be increased by a factor of two using optical diffraction. A similar visibility limit occurs for crystalline protrusions at a crystal/amorphous interface. The visibility limit is affected by defocus, and at -60.0 nm defocus a crystalline protrusion of Pd 3Si can become more visible due to a zero in the microscope contrast transfer function at the nearest-neighbor bond distance of the amorphous alloy. The atomic arrangement of crystalline Pd 3Si extends a few atomic diameters into the amorphous matrix for a crystal/amorphous interface constructed with the DRP model, and this structure can be observed by HRTEM.